Multi-component alloy products and the methods of making thereof

ABSTRACT

Various embodiments of multi-component products are provided herein, with specific reference to methods of making the same. In some embodiments, the present invention is a method that includes feeding a heated gas to a powder feeder containing a powder having an element, spraying the powder from the powder feeder through a nozzle onto a surface of a substrate at a sufficient velocity to form a multi-component deposit on the substrate, and directing an energy beam from an energy source at the multi-component deposit to heat the multi-component deposit until the multi-component deposit is fixed to the substrate thereby forming a multi-component alloy coating on the substrate.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of International Patent App. No. PCT/US2018/020014, filed Feb. 27, 2018, which claims benefit of U.S. provisional application no. 62/464,562, filed Feb. 28, 2017 and claims benefit of U.S. provisional application no. 62/464,094, filed Feb. 27, 2017, each of which are herein incorporated by reference in its entirety.

BACKGROUND

Products with tailored properties and/or varying compositions are difficult to manufacture.

FIELD OF THE INVENTION

Broadly, the present disclosure is directed towards methods of making multi-component alloy products. More specifically, the present disclosure is directed towards methods of making multi-component alloy products and multi-component alloy products having anti-microbial properties.

SUMMARY OF THE DISCLOSURE

The figures constitute a part of this specification and include illustrative embodiments of the present disclosure and illustrate various objects and features thereof. In addition, any measurements, specifications and the like shown in the figures are intended to be illustrative, and not restrictive. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for teaching one skilled in the art to variously employ the present invention.

Among those benefits and improvements that have been disclosed, other objects and advantages of this invention will become apparent from the following description taken in conjunction with the accompanying figures. Detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely illustrative of the invention that may be embodied in various forms. In addition, each of the examples given in connection with the various embodiments of the invention is intended to be illustrative, and not restrictive.

Throughout the specification and claims, the following terms take the meanings explicitly associated herein, unless the context clearly dictates otherwise. The phrases “in one embodiment” and “in some embodiments” as used herein do not necessarily refer to the same embodiment(s), though it may. Furthermore, the phrases “in another embodiment” and “in some other embodiments” as used herein do not necessarily refer to a different embodiment, although it may. Thus, as described below, various embodiments of the invention may be readily combined, without departing from the scope or spirit of the invention.

In addition, as used herein, the term “or” is an inclusive “or” operator, and is equivalent to the term “and/or,” unless the context clearly dictates otherwise. The term “based on” is not exclusive and allows for being based on additional factors not described, unless the context clearly dictates otherwise. In addition, throughout the specification, the meaning of “a,” “an,” and “the” include plural references, unless the context clearly dictates otherwise. The meaning of “in” includes “in” and “on”, unless the context clearly dictates otherwise.

In some embodiments, the present invention is a method comprising feeding a heated gas to a powder feeder; wherein the powder feeder comprises a powder; wherein the powder comprises an element; spraying the powder from the powder feeder through a nozzle onto a surface of the substrate at a sufficient velocity to form a multi-component deposit on the substrate; and directing an energy beam from an energy source at the multi-component deposit to heat the multi-component deposit until the multi-component deposit is fixed to the substrate, thereby forming a multi-component coating on the substrate. Without being bound by any mechanism or theory, in embodiments, the fixing of the multi-component deposit to the substrate may be a result of the elementally combining the multi-component deposit and the substrate.

In one or more of the described embodiments, the method further comprises feeding the heated gas to a plurality of powder feeders. In one or more embodiments, the heated gas is heated to a temperature below the melting point of the powder in the powder feeders.

In one or more of the described embodiments, the plurality of powder feeders includes at least two, at least three, less than eight or less than nine powder feeders. In one or more of the described embodiments, the plurality of powder feeders includes two, three, four, five, six, seven, eight, or nine powder feeders. In one or more of the described embodiments, the plurality of powder feeders includes at least one of: two to nine, two to seven, two to five, four to nine, five to nine, or seven to nine powder feeders.

In one or more of the described embodiments, each of the plurality of powder feeders comprises a powder of an element. In one or more of the described embodiments, the powder may contain one or more of the following elements: aluminum (Al), silicon (Si), lithium (Li), any useful element of the alkaline earth metals, any useful element of the transition metals, any useful element of the post-transition metals, and any useful element of the rare earth elements. As used herein, useful elements of the alkaline earth metals are beryllium (Be), magnesium (Mg), calcium (Ca), and strontium (Sr). As used herein, useful elements of the transition metals are titanium (Ti), vanadium(V), chromium(Cr), manganese(Mn), iron(Fe), cobalt (Co), nickel (Ni), zinc (Zn), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), platinum (Pt), or gold (Au). As used herein, useful elements of the post-transition metals are gallium (Ga), germanium (Ge), indium (In), tin (Sn), lead (Pb) or bismuth (Bi). As used herein, useful elements of the rare earth elements are scandium, yttrium and any of the fifteen lanthanides elements. The lanthanides are the fifteen metallic chemical elements with atomic numbers 57 through 71, from lanthanum through lutetium.

In one or more of the described embodiments, the powder may include a plurality of elements. For elements that are not easily atomized or deposited, in one or more of the described embodiments, the elements may be combined with at least one element that is more readily atomized or deposited. In a non-limiting example, the powder may include tungsten, an element that is not easily atomize or deposited, and aluminum, an element that is more readily atomized and deposited.

In one or more of the described embodiments, the powder may include one or more grain refiners. As used herein, “grain refiner” means a nucleant or nucleants that facilitates aluminum crystal formation. Suitable grain refiners include ceramic materials, intermetallic materials, and combinations thereof, among others.

In one approach, a ceramic material is used to facilitate grain refinement. Examples of

ceramics include oxide materials, boride materials, carbide materials, nitride materials, silicon materials, carbon materials, and/or combinations thereof. Some additional examples of ceramics include metal oxides, metal borides, metal carbides, metal nitrides and/or combinations thereof.

Additionally, some non-limiting examples of ceramics include: TiB, TiB2, TiC, SiC, Al2O3, BC, BN, Si3N4, Al4C3, AlN, their suitable equivalents, and/or combinations thereof.

In one or more of the described embodiments, the average particle size of the powder may include any particle size suitable for spraying the powder onto a substrate as detailed herein.

In one or more of the described embodiments, each of the plurality of powder feeders comprises a powder of a plurality of elements. In one or more of the described embodiments, the plurality of powder feeders comprises powders of elements of a multi-component alloy.

In one or more of the described embodiments, the velocity of the powder sufficient for depositing on the substrate is at least one of: 100 m/s to 1,200 m/s, 100 m/s to 1,100 m/s, 100 m/s to 1,000 m/s, 100 m/s to 900 m/s, 100 m/s to 800 m/s, 100 m/s to 700 m/s, 100 m/s to 600 m/s, 100 m/s to 500 m/s, 100 m/s to 400 m/s, 100 m/s to 300 m/s, 100 m/s to 200 m/s, at least 100 m/s, less than 1,200 m/s, less than 1,000 m/s, or less than 900 m/s.

In one or more of the described embodiments, the substrate is an aluminum alloy. In one or more of the described embodiments, the substrate is a titanium alloy. In one or more of the described embodiments, the substrate is an iron alloy. In one or more of the described embodiments, the substrate is a nickel alloy. In one or more of the described embodiments, the substrate is a cobalt alloy. In one or more of the described embodiments, the substrate is a multi-component alloy.

In one or more of the described embodiments, the method further comprises spraying a plurality of powders through one nozzle onto a surface of the substrate; wherein the plurality of powders comprise elements of a multi-component alloy.

In one or more of the described embodiments, the method further comprises directing an energy beam from an energy source at the substrate to heat the substrate below a solidus temperature of the substrate. Without being bound by any mechanism or theory, the heating of the substrate softens the substrate and increase adhesion of the sprayed powders.

In one or more of the described embodiments, the method further comprises comprising spraying a plurality of powders through a plurality of nozzles (e.g. wherein each nozzle is configured to spay/direct a powder); wherein, during the spraying step, a first nozzle of the plurality of nozzles is closed and a second nozzle of the plurality of nozzles is open. In one or more of the described embodiments, the method includes opening and/or closing the nozzles to tailor the powder composition so as to form a multi-component coating having at least one of a single multi-component alloy composition, a blend of at least two multi-component alloy compositions, a gradient composition, a location-dependent composition (e.g. location 1 is configured with coating of powder A, location 2 is configured with coating of powder B, location 3 positioned between 1 and 2 is configured with a gradient or blended powder), and/or combinations thereof.

In one or more of the described embodiments, the energy beam from the energy source may include at least one of: a laser beam or an electron beam. In one or more of the described embodiments, the energy beam from the energy source may include a laser and an electron beam. In one or more of the described embodiments, the energy beam from the energy source may include a laser sintering device.

In one or more of the described embodiments, the coated substrate comprises a multi-component alloy coating on a portion of the surface of the substrate. In one or more of the described embodiments, the coated substrate comprises a single multi-component alloy coating. In one or more of the described embodiments, the coated substrate comprises a gradient multi-component alloy coating. In one or more of the described embodiments, the coated substrate comprises a blended multi-component alloy coating.

In one or more of the described embodiments, the method further comprises repeating the feeding, spraying and directing steps to form a plurality of multi-component alloy coatings on the substrate. In one or more of the described embodiments, the method further comprises repeating the feeding, spraying and directing steps to form at least one of: two, three, four, five, six, seven, eight, two to eight, two to six, two to four, four to eight, six to eight, at least two, or less than eight multi-component alloy coatings on the substrate.

In one or more of the described embodiments, at least one of the plurality of powder feeders comprises a powder of silver-containing material. As used herein, the phrase “silver-containing material” includes material that contains an amount of silver, e.g., a sufficient amount of silver to impart anti-microbial properties. In one or more of the described embodiments, the method further comprises spraying the powder of silver-containing material onto the substrate to form a silver-containing material deposit.

In one or more of the described embodiments, further comprising directing the energy beam from the energy source at the silver-containing material deposit to form a silver-containing material coating; wherein the silver-containing material coating comprises a first portion and a second portion, wherein the first portion and the second portion are not adjacent to each other.

In one or more of the described embodiments, the silver-containing material coating comprises at least one of an AgXAlCoCrCuNi alloy or an AgXAlCoCrCuFeNi alloy; wherein X is a weight percent of Ag in the alloy. In one or more of the described embodiments, the substrate comprises at least one of an AlCoCrCuNi alloy or an AlCoCrCuFeNi alloy. In one or more of the described embodiments, the silver-containing material coating comprises at least one of an AgXAlCoCrCuNi alloy or an AgXAlCoCrCuFeNi alloy; wherein X is a weight percent of Ag in the alloy; and the substrate comprises at least one of an AlCoCrCuNi alloy or an AlCoCrCuFeNi alloy.

In one or more of the described embodiments, at least one of the first portion or the second portion comprises silver in a sufficient amount to improve an antimicrobial property of the substrate compared to an uncoated substrate. As used herein, “anti-microbial” or “anti-microbial property” refers to a composition that reduces the proliferation of or kills microbial organisms, e.g., but not limited to, bacteria, protozoa, fungi, and the like.

In an embodiment, the method comprises feeding a heated gas to a plurality of powder feeders; wherein each of the powder feeders comprises a powder of an element; spraying the powders from the powder feeders to a mixing chamber to form a multi-component mixture; spraying the multi-component mixture through a nozzle onto a surface of the substrate at a sufficient velocity to form a multi-component deposit on the substrate; and directing an energy beam from an energy source at the multi-component deposit to heat the multi-component deposit until the multi-component deposit is fixed to the substrate, thereby forming a multi-component alloy coating on the substrate.

In an embodiment, the system comprises a spraying device configured to spray a powder of an element onto a substrate; a nozzle; a powder feeder; a gas supply; a gas heater; and an energy source configured to direct an energy beam at the powder so as to form a multi-component alloy coating on the substrate. In one or more of the described embodiments, the spraying device include the nozzle. In one or more of the described embodiments, the spraying device is a cold spray forming gun having at least one nozzle. In one or more of the described embodiments, the spraying device is configured to spray a plurality of powders onto a substrate.

In one or more of the described embodiments, the system comprises a plurality of nozzles. In one or more of the described embodiments, the system includes a plurality of nozzles. In one or more of the described embodiments, the system includes at least one of: two, three, four, five, six, seven, eight, nine, two to nine, two to seven, two to five, four to nine, five to nine, seven to nine, at least two and less than nine nozzles. In one or more of the described embodiments, the spraying device comprises the plurality of nozzles.

In one or more of the described embodiments, the nozzle is configured to deliver the powder. In one or more of the described embodiments, the nozzle is tailored to deliver the powder so as to form a multi-component deposit on the substrate.

In one or more of the described embodiments, the nozzle comprises at least one of a converging section or a diverging section. In one or more of the described embodiments, the nozzle comprises at least one of a converging section or a diverging section. In one or more of the described embodiments, the nozzle comprises a converging section. In one or more of the described embodiments, the nozzle comprises a diverging section. In one or more of the described embodiments, the nozzle comprises a converging section and a diverging section.

In one or more of the described embodiments, the gas supply comprises a substantially non-reactive gas. In one or more of the described embodiments, the gas supply comprises an inert gas. In one or more of the described embodiments, the gas supply comprises a substantially reactive gas (e.g. participates/interacts in coating process to form coated article/product). Some non-limiting examples of a gas include: at least one of nitrogen, helium, argon, or combinations thereof. In some embodiments, the gas supply comprises a reactive gas such as a nitrogen containing gas, a boron containing gas, or pressured gas of atmospheric composition (e.g. oxygen-containing gas).

In one or more of the described embodiments, the system is configured based, at least in part, on the velocity of the powder required to deposit on the substrate. In one or more of the described embodiments, the system is configured to supply a gas at a sufficient pressure to achieve the sufficient velocity of the powder required to deposit on the substrate.

In one or more of the described embodiments, the system comprises one nozzle and a mixing chamber located between the nozzle and the plurality of powder feeders. In embodiments, the mixing chamber is configured to mix the plurality of powders before entering the nozzle. In embodiments, the system comprises a plurality of mixing chambers. In embodiments, the plurality of mixing chambers includes at least one of two, three, four, five, two to five, two to four, three to five, at least two, and less than five mixing chambers.

In one or more of the described embodiments, the system further comprises a plurality of energy beams from the energy sources; wherein at least one energy beam from an energy source is configured for heating the substrate to a temperature below the solidus temperature of the substrate and/or wherein at least one of the plurality of the energy beams from an energy sources is configured to heat the multi-component deposit sufficiently to fix the multi-component deposit to the substrate thereby forming a multi-component alloy coating on the substrate. In one or more of the described embodiments, the system further comprises at least one of two, three, four, five, six, seven, eight, two to eight, two to six, two to four, four to eight, six to eight, at least two, or less than energy beams from energy sources.

In one or more of the described embodiments, the plurality of energy beams from the energy sources are directed to one area on the surface of the substrate to form a coating. In one or more of the described embodiments, the system is configured so the energy beams from the energy sources may travel across a surface of the substrate sufficiently so as to form a multi-component alloy coating having at least one of a single multi-component alloy composition, a blend of at least two multi-component alloy compositions, or a gradient composition.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments of the present invention, briefly summarized above and discussed in greater detail below, can be understood by reference to the illustrative embodiments of the invention depicted in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.

FIG. 1 depicts a schematic view of an exemplary system for depositing a multi-component alloy powder onto a substrate in accordance with some embodiments of the present disclosure.

FIG. 2A depicts a schematic view of an exemplary system for depositing a multi-component alloy powder onto a substrate in accordance with some embodiments of the present disclosure.

FIG. 2B depicts a schematic view of an exemplary system for depositing a multi-component alloy powder onto a substrate in accordance with some embodiments of the present disclosure.

FIG. 3A depicts a schematic view of an exemplary overall system diagram of an exemplary controller system in accordance with some embodiments of the present disclosure.

FIG. 3B depicts a schematic view of an exemplary control system guided user interface (GUI) in which the user can control the various elements that are included in exemplary system to create a desired multi-component alloy.

FIG. 3C depicts a schematic view of an exemplary control system GUI in which the user can control the various elements that are included in exemplary system to create a desired multi-component alloy.

FIG. 4 depicts a schematic view of an exemplary control system configured to control the various elements of the method in accordance with some embodiments of the present disclosure.

FIG. 5 depicts critical velocities for different elements and materials.

FIG. 6 depicts an exemplary configuration of a multi-component alloy product produced by the method in accordance with some embodiments of the present disclosure.

FIG. 7 depicts an exemplary configuration of a multi-component alloy product produced by the method in accordance with some embodiments of the present disclosure.

FIG. 8 depicts an exemplary configuration of a multi-component alloy product produced by the method in accordance with some embodiments of the present disclosure.

FIG. 9 depicts an exemplary configuration of a multi-component alloy product produced by the method in accordance with some embodiments of the present disclosure.

To facilitate understanding, identical reference numerals have been used, where possible, to designate identical elements that are common to the figures. The figures are not drawn to scale and may be simplified for clarity. It is contemplated that elements and features of one embodiment may be beneficially incorporated in other embodiments without further recitation.

DETAILED DESCRIPTION

The figures constitute a part of this specification and include illustrative embodiments of the present invention and illustrate various objects and features thereof. The drawings shown are not necessarily to scale, with emphasis instead generally being placed upon illustrating the principles of the present invention. Further, some features may be exaggerated to show details of particular components. In addition, any measurements, specifications and the like shown in the figures are intended to be illustrative, and not restrictive. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for teaching one skilled in the art to variously employ the present invention.

Throughout the specification, the following terms take the meanings explicitly associated herein, unless the context clearly dictates otherwise. The phrases “in one embodiment” and “in some embodiments” as used herein do not necessarily refer to the same embodiment(s), though it may. Furthermore, the phrases “in another embodiment” and “in some other embodiments” as used herein do not necessarily refer to a different embodiment, although it may. Thus, as described below, various embodiments of the invention may be readily combined, without departing from the scope or spirit of the invention.

In addition, as used herein, the term “or” is an inclusive “or” operator, and is equivalent to the term “and/or,” unless the context clearly dictates otherwise. The term “based on” is not exclusive and allows for being based on additional factors not described, unless the context clearly dictates otherwise. In addition, throughout the specification, the meaning of “a”, “an”, and “the” include plural references. The meaning of “in” includes “in” and “on”.

As used herein, the term “at least one of A, B, or C” and the like, means “only A”, “only B”, “only C”, or “any combination of A, B, and C.”

Methods and Systems for Making Multicomponent Alloy Products

In some embodiments, the present disclosure relates to an exemplary system for depositing a multi-component alloy powder onto a substrate. In some embodiments, the present disclosure relates to an exemplary method for depositing a multi-component alloy powder onto a substrate. In some embodiments, the present invention allows the ability to adjust multi-component alloy coatings by changing one or more powders.

In some embodiments, the present invention provides for an exemplary system for depositing a multi-component alloy powder onto a substrate that includes at least: (a) a multi-nozzle cold spray forming gun for simultaneously spraying an at least one element powder on the substrate; (b) an at least one powder feeder; (c) a gas supply; (d) a gas heater; or (e) an energy beam from an energy source for fixing the at least one element powder to the substrate.

In some embodiments, the present invention provides for an exemplary method for depositing a multi-component alloy powder onto a substrate that includes at least: (a) optionally, selecting a substrate on which powder elements will be to form a multi-component alloy coating; (b) optionally, heating a gas heater to a predetermined temperature from user inputs in a control system GUI stored in a control system database; (c) initiating a gas supply to desired powder feeders as determined from user inputs in the control system GUI; (d) spraying powders elements from the desired powder feeders onto the substrate for a predetermined amount of time to form a multi-component deposit; and (e) directing an energy beam from an energy source at the multi-component deposit to heat the multi-component deposit until the multi-component deposit and the substrate are elementally combined such that the multi-component alloy coating is fixed onto the substrate. In some embodiments, the exemplary method can be utilized to provide multiple passes over the same areas of a substrate to build a gradient multi-component alloy.

FIG. 1 depicts an exemplary system 100 for depositing a multi-component alloy powder onto a substrate in accordance with some embodiments of the present disclosure. In some embodiments, the substrate can be a multi-component alloy, for example an aluminum substrate with multiple powders to create a multi-component alloy at the surface. In some embodiments, the substrate can be a glass substrate or a metal substrate (e.g. examples of elemental metals and alloys, as set out above).

As used herein, “multi-component alloy”, “multi-component alloy product” and the like means a product with a metal matrix, where at least four different elements making up the matrix, and where the multi-component product comprises 5-35 at. % of the at least four elements. In one embodiment, at least five different elements make up the matrix, and the multi-component product comprises 5-35 at. % of the at least five elements. In one embodiment, at least six different elements make up the matrix, and the multi-component product comprises 5-35 at. % of the at least six elements. In one embodiment, at least seven different elements make up the matrix, and the multi-component product comprises 5-35 at. % of the at least seven elements. In one embodiment, at least eight different elements make up the matrix, and the multi-component product comprises 5-35 at. % of the at least eight elements. As described below, additives may also be used relative to the matrix of the multi-component alloy product.

In one embodiment, as depicted in FIG. 1, the exemplary system 100 comprises a multi-nozzle cold spray forming gun 102. In some embodiments, multi-nozzle cold spray forming gun 102 has at least two nozzles 114. In some embodiments, the multi-nozzle cold spray forming gun 102 simultaneously sprays an at least one element powder (e.g. depicted as “HEA Powder Mixture” in FIG. 1) from the nozzles 114 onto the substrate. In some embodiments, a non-limiting example of a multi-nozzle cold spray forming gun 102 is depicted in U.S. Pat. No. 8,544,769.

The exemplary system 100 further comprises an at least one powder feeder 104. In some embodiments, the number of powder feeders 104 in the exemplary system 100 is equivalent to the number of nozzles 114. In some embodiments, each of the powder feeders 104 is fluidly coupled to one of the nozzles 114 via third pipes 120. In some embodiments, one powder feeder 104 can be fluidly coupled to multiple nozzles 114. In some embodiments, one nozzle 114 can be coupled to multiple powder feeders 104.

In one embodiment, as depicted in FIG. 1, the exemplary system 100 comprises five powder feeders 104 and five nozzles 114. Other embodiments of the exemplary system 100 may contain more or less than five powder feeders 104 and equivalent more or less than five nozzles 114 (i.e. a non-zero number limited by for example, design, technology, cost, size or a combination thereof). In some embodiments, the at least one powder feeder 104 comprises a single metal element powder or a mixture of metal powders.

In some embodiments, the powder feeders 104 contain a single element powder. In some embodiments, the single element powder in each powder feeder 104 can be different. In some embodiments, the single element powder in some of the powder feeders 104 of the exemplary system 100 can be different from the single element powder in some of the other powder feeders 104 of the exemplary system 100 while being the same as the single element powder in yet other powder feeders 104 of the system.

In some embodiments, the powder feeders 104 contain a mixture of powders. In some embodiments, the mixture of powders in each powder feeder 104 can be different. In some embodiments, the mixture of powders in some of the powder feeders 104 of the exemplary system 100 can be different from the mixture of powders in some of the other powder feeders 104 of the exemplary system 100 while being the same as the mixture of powders in yet other powder feeders 104 of the system.

In some embodiments, some of the powder feeders 104 of the exemplary system 100 can be a single element powder while some of the powder feeders 104 of the exemplary system 100 can be a mixture of powders. In some embodiments, in the manner described above, the single element powder in the powder feeders 104 can be the same as other single element powders in the powder feeders 104 of the exemplary system 100 or some of the single element powder in the powder feeders 104 can be the same as other single element powders while being different from yet other single element powders in the exemplary system 100.

In one embodiment, as depicted in FIG. 1, the exemplary system 100 comprises a gas supply 106. In some embodiments, the gas supply 106 is fluidly coupled via first pipes 112 to each of the at least one powder feeder 104. In some embodiments, the gas supply 106 provides a suitable gas, including but not limited to nitrogen or helium, to each of the at least one powder feeders 104. In some embodiments, the gas supply 106 provides a reactive gas such as a nitrogen containing gas or a boron containing gas that can for example, nitrodize or boridize the powders. In embodiments, the gas from the gas supply 106 forces the powders from each of the powder feeders 104, into the cold spray forming gun 102 and out of the associated nozzle 114 simultaneously. In some embodiments, “duty cycles” of the spray nozzles can determine the amount of powder sprayed from the nozzles 114 versus just the gas pressure provided by the gas supply. In some embodiments, simultaneous spraying of the powders from the nozzles 114 allows the powders to mix, thus creating a multi-component alloy on a desired substrate. In some embodiments, the velocities at which the powders exit the nozzles 114 allow them to be applied to a desired substrate 116.

In one embodiment, as depicted in FIG. 1, the exemplary system 100 comprises a gas heater 108. The gas heater 108 is fluidly coupled to the gas supply 106 via second pipe 118. In some embodiments, the gas heater 108 is connected to each individual third pipes 120 from a powder feeder 104 to its associated nozzle 114. In some embodiments, the gas heater 108 heats the powder in the third pipes 120 prior to release from the nozzles 114.

In one embodiment, as depicted in FIG. 1, the exemplary system 100 comprises a laser sintering device 110 (i.e., a non-limiting example of an energy beam from an energy source) for permanently fixing the at least one element powder to the substrate 116 to form a multi-composite alloy 122 on the substrate 116.

In one embodiment, as depicted in FIG. 1, the exemplary system 100 comprises an exemplary controller system 124. The exemplary controller system 124 is configured to control the gas heater 108, the gas supply 106, and each nozzle 114.

FIGS. 2A and 2B depict exemplary systems for depositing a multi-component alloy powder onto a substrate in accordance with some embodiments of the present disclosure.

FIG. 2A is an exemplary system that includes a low pressure gas supply, a gas heater, a powder feeder and a nozzle. In the exemplary system shown in FIG. 2A, the low pressure gas supply is first heated using the gas heater and then the heated gas is conveyed to the nozzle. The powder is then fed into the heated gas at the nozzle using the powder feeder. The powder-containing gas is then sprayed on a substrate to form a deposit.

FIG. 2B is a system that includes a high pressure gas supply, a gas heater, a powder feeder and a nozzle (depicted as a de laval nozzle in FIG. 2B). In the exemplary system shown in FIG. 2B, a first portion of the high pressure gas supply is heated in the gas heater to form a heated gas. A second portion of the high pressure gas supply is conveyed to a powder feeder to form a powder-containing gas. The heated gas is then mixed with the powder-containing gas, conveyed through a nozzle and then sprayed on the substrate to form a deposit.

In non-limiting embodiments, the system may include a combination of systems detailed in FIGS. 1, 2A, and 2B. In embodiments, the system may include a low pressure gas supply system shown in FIG. 2A and a high pressure gas supply system shown in FIG. 2B. In other embodiment, the system may include a plurality of low pressure gas supply systems shown in FIG. 2A and a plurality of high pressure gas supply systems shown in FIG. 2B.

FIG. 3A depicts an exemplary overall system diagram of an exemplary controller system 124 in accordance with some embodiments of the current disclosure. The exemplary controller system 124 includes a control system guided user interface (GUI) which allows a user to input parameters for the multi-nozzle cold spray forming gun 102. In some embodiments, the user can input parameters including but not limited to velocity, pressure, temperature, and distance. In some embodiments, the GUI allows the user to control each individual powder feeder which can contain one or more elements. In some embodiments, the GUI also allows the user to select an element and the amount of that element that is being added to the substrate. In some embodiments, the user inputs are stored in the control system database. In some embodiments, storing the user inputs in the control system database allows the inputs to be saved in order for the control system base software to provide desired actions to the specific control system controllers. In an exemplary embodiment of FIG. 3A, the control system base software controls the powder feeder 1 controller, powder feeder 2 controller, powder feeder 3 controller, powder feeder 4 controller, powder feeder 5 controller, gas supply controller and the gas heater controller which are also included in the exemplary controller system 124.

FIGS. 3B-3C depict an exemplary control system GUI in which the user can control the various elements that are included in exemplary system 100 in order to add a controlled amount of the elements to the substrate in order to create a desired multi-component alloy in accordance with some embodiments of the present disclosure.

FIG. 3B depicts an exemplary control system GUI that includes, in some embodiments, the powder feeder controls, gas supply controls, and options. In some embodiments, the powder feeder controls allow the user to select which powder feeder should be on or off In some embodiments, the gas supply controls allow the user to turn the gas supply and the gas heater on or off. In some embodiments, the options allow the user to adjust the settings for the nozzles (spray nozzle), gas heater settings, and powder feeder settings. Once the user has selected the desired inputs and selects the save button, the settings may be stored in the control system database.

FIG. 3C depicts an exemplary options menu which, in some embodiments, allows the user to adjust the distance and velocity of the nozzle, the desired temperature of the gas heater, and the pressure and the elements in the various powder feeders. In some embodiments, once the user selects the desired settings, the user can select save in order to store the settings into the control system database and returns to the GUI in FIG. 3B. In other embodiments, the process parameters are based, at least in part, on

FIG. 4 depicts an exemplary logical diagram utilized to program an exemplary process control system base software which, in some embodiments, controls the various elements of the cold spray process in accordance with some embodiments of the present disclosure. In some embodiments, an exemplary process 400 begins at step 402 by the user selecting the various inputs in the control system GUI. In some embodiments, at step 404 the inputs are stored in the control system database. In some embodiments, at step 406 the gas heater is initiated to a predetermined temperature (from the control system database) and at step 408 the gas (e.g. helium or nitrogen) is activated to supply the desired powder feeders (from the control system database). In some embodiments, at step 410, the cold spray process is initiated for a predetermined amount of time. The gas supply pushes the powder in the desired feeders into the various nozzles and into the gas heater. The heated gas, which is heated below the melting point of the powder, forces the powder onto the substrate. The steps of the exemplary method 400 produce a multi-component alloy on the substrate by applying various powder elements to the substrate simultaneously. In some embodiments, at step 412, a laser sintering process is activated and the newly produced multi-component alloy is permanently fixed to the substrate. In some embodiments, at step 414, the cold spray process, gas supply, and the gas heater are deactivated. In some embodiments, at step 416 the laser sintering process is deactivated.

As detailed herein, the spraying powder step is conducted so as to result in a sufficient powder velocity to allow for deposition of the powder on the substrate. In embodiments, the sufficient powder velocity corresponds to the highest critical velocity for each element in the powder. As used herein, the term “critical velocity” of an element or material is the velocity above which the element or material will deposit on a surface.

FIG. 5 shows non-limiting examples of critical velocities for different elements and materials. Notably, although FIG. 5 depicts a non-limiting average particle size of 25 microns, the powder may include any particle size suitable for spraying the powder onto a substrate as detailed herein. Further, the dark grey section of each bar on FIG. 5 corresponds to the uncertainty associated with each critical velocity. Thus, the critical velocity for magnesium (Mg) ranges from about 800 m/s to about 850 m/s.

In one or more embodiments detailed herein, the sufficient powder velocity may be achieved by adjustment of at least one of: nozzle design, powder material, gas temperature or gas pressure.

Antimicrobial Multi-Component Alloy Products

The methods of making multi-component alloy products detailed herein may also be used to make multi-component alloy products having antimicrobial properties.

As used herein, “anti-microbial” refers to a composition that reduces the proliferation of or kills microbial organisms, e.g., but not limited to, bacteria, protozoa, fungi, and the like.

FIGS. 6 and 7 show embodiments of the multi-component alloy product produced by methods of the present invention, comprising a first portion devoid of silver (e.g. 2 example compositions provided in the schematics of FIGS. 6 and 7) and a second portion containing silver, where “X” amount of silver (wt %) is present in the second portion. In one embodiment, X is from 0.01 to 2 wt %. In another embodiment, X is from 0.01 to 1.5 wt %. In another embodiment, X is from 0.01 to 1.0 wt %. In another embodiment, X is from 0.01 to 0.5 wt %. In another embodiment, X is at least 0.01 wt %. In another embodiment, X is less than 2 wt %. The first portion, comprising a multi-component alloy, contains no anti-microbial metals, exhibits no anti-microbial properties, but has a functional use in an application where anti-microbial properties are desired. A layer of silver (e.g., pure or alloyed) is deposited on the surface of the first portion (as shown in FIG. 6) using one or more methods detailed herein, and can then be annealed (e.g., using a laser annealing process, for example) to the first portion (as shown in FIG. 7), creating a functional gradient from the first portion to the silver-containing material (second portion). The resulting material may exhibit the mechanical, electrical, thermal properties of the first portion, while simultaneously exhibiting the anti-microbial properties of the silver-containing material coating (second portion). In some embodiments, the multicomponent alloy may comprise an alloy disclosed in Hsu et al., “Alloying behavior of iron, gold and silver in AlCoCrCuNi-based equimolar high-entropy alloys” (2007) 460-461:403-408.

FIG. 8 shows an embodiment of an exemplary composition comprising a first portion, wherein the first portion is a multi-component alloy comprising a percentage of silver (an “X” amount of silver (wt %), where the first portion includes, but is not limited to, AgXAlCoCrCuNi) which does not confer an anti-microbial property, and a second portion, wherein the second portion is a multi-component alloy comprising a percentage of silver which does confer an anti-microbial property (an “X”+10 wt % amount of silver, e.g., where if X is 2 wt % silver in the first portion, the second portion will generally have about 12 wt % silver). In this example, the first portion and the second portion contain the same elements (e.g., but not limited to, AgXAlCoCrCuNi), but has an increased weight % of silver 10%, 10.5%, 11%, 11.5%, 12%) Accordingly, the composition exhibits anti-microbial properties and may have a gradient of silver where the first portion and the second portion meet.

FIG. 9 shows an embodiment of an exemplary composition comprising a first portion, wherein the first portion is a first multi-component alloy (e.g., but not limited to, AlCoCrCuNi), and a plurality of second portions, wherein the plurality of second portions are second multi-component alloys (e.g., but not limited to, AgXAlCoCrCuNi). In some embodiments, each second portion of the plurality of second portions is not adjacent to each other. In some embodiments, the first portion comprises silver in a sufficient amount to confer anti-microbial properties. In some embodiments, the first portion does not comprise silver in a sufficient amount to confer anti-microbial properties. In some embodiments, each second portion of the plurality of second portions is affixed to the first portion (e.g., but not limited to, being affixed by annealing, etc.) In some embodiments, the composition is configured to exhibit at least two levels of anti-microbial properties (e.g., as a non-limiting illustration, a first portion can exhibit 80% anti-microbial properties while a second portion can exhibit 98% anti-microbial properties.)

Without being bound by mechanism or theory, the methods of the present invention allow for a precise tailoring of surface regions so as to result in an multi-component alloy product having anti-microbial properties.

In some embodiments, another exemplary composition can include (1) at least one first portion, wherein the first portion has a surface, and (2) a plurality of anti-microbial portions, wherein the plurality of anti-microbial portions are adhered to the surface of the at least one first portion. In some embodiments, each of the anti-microbial portions of the plurality of anti-microbial portions is identical in composition. In some embodiments, each of the anti-microbial portions of the plurality of anti-microbial portions is not identical in composition to remaining anti-microbial portions of the plurality of anti-microbial portions.

While various embodiments of the present invention have been described in detail, it is apparent that modifications and adaptations of those embodiments will occur to those skilled in the art. However, it is to be expressly understood that such modifications and adaptations are within the spirit and scope of the present invention. 

What is claimed is:
 1. A method comprising: (a) feeding a heated gas to a powder feeder; wherein the powder feeder comprises a powder; wherein the powder comprises an element; (b) spraying the powder from the powder feeder through a nozzle onto a surface of a substrate at a sufficient velocity to form a multi-component deposit on the substrate; and (c) directing an energy beam from an energy source at the multi-component deposit to heat the multi-component deposit until the multi-component deposit is fixed to the substrate, thereby forming a multi-component alloy coating on the substrate.
 2. The method of claim 1, wherein the method comprises: (a) feeding the heated gas to a plurality of powder feeders.
 3. The method of claim 2, wherein each of the plurality of powder feeders comprises a powder of an element.
 4. The method of claim 2, wherein each of the plurality of powder feeders comprises a powder of a plurality of elements.
 5. The method of claim 1, wherein the sufficient velocity of the powder is 100 m/s to 1,000 m/s.
 6. The method of claim 1, wherein the substrate is an aluminum alloy.
 7. The method of claim 1, wherein the substrate is a multi-component alloy.
 8. The method of claim 1, further comprising spraying a plurality of powders through one nozzle onto a surface of the substrate; wherein the plurality of powders comprise elements of a multi-component alloy.
 9. The method of claim 1, further comprising directing the energy beam from the energy source at the substrate to heat the substrate below a solidus temperature of the substrate.
 10. The method of claim 1, further comprising spraying a plurality of powders through a plurality of nozzles; wherein, during the spraying step, a first nozzle of the plurality of nozzles is closed and a second nozzle of the plurality of nozzles is open.
 11. The method of claim 1, further comprising repeating steps (a) to (c) to form a plurality of multi-component alloy coatings on the substrate.
 12. The method of claim 2, wherein at least one of the plurality of powder feeders comprises a powder of silver-containing material.
 13. The method of claim 12, further comprising spraying the powder of silver onto the substrate to form a deposit comprising silver-containing material.
 14. The method of claim 13, further comprising directing the energy beam from the energy source at the deposit comprising silver-containing material to form a coating comprising silver-containing material; wherein the coating comprising silver-containing material comprises a first portion and a second portion, wherein the first portion and the second portion are not adjacent to each other.
 15. The method of claim 14, wherein at least one of the first portion or the second portion comprises silver in a sufficient amount to improve an antimicrobial property of the substrate compared to an uncoated substrate.
 16. A method comprising: (a) feeding a heated gas to a plurality of powder feeders; wherein each of the powder feeders comprises a powder of an element; (b) spraying the powders from the powder feeders to a mixing chamber to form a multi-component mixture; (c) spraying the multi-component mixture through a nozzle onto a surface of a substrate at a sufficient velocity to form a multi-component deposit on the substrate; and (d) directing an energy beam from an energy source at the multi-component deposit to heat the multi-component deposit until the multi-component deposit is fixed to the substrate, thereby forming a multi-component alloy coating on the substrate.
 17. A system comprising: (a) a spraying device configured to spray a powder of an element onto a substrate; (b) a nozzle; (c) a powder feeder; (d) a gas supply; (e) a gas heater; and (f) an energy source configured to direct an energy beam at the powder so as to form a multi-component alloy coating on the substrate.
 18. The system of claim 17, further comprising a plurality of nozzles.
 19. The system of claim 17, wherein the nozzle comprises at least one of a converging section or a diverging section.
 20. The system of claim 17, further comprising a plurality of energy sources; wherein at least one of the plurality of energy sources is configured for heating the substrate to a temperature below the solidus temperature of the substrate. 